In this study, [Ru(bpy)2(tbtp)](PF6)23.75H2O, 1  (where bpy = 2,2'-bipyridine and tbtp = 4,5,9,11,14-pentaaza-benzo<b>triphenylene) was reacted with [Co(dmgBF2)2(H2O)2] (where dmgBF2 = difluorboryldimethylglyoximato) to yield the mixed-metal binuclear complex, [Ru(bpy)2(tbtp)Co(dmgBF2)2(H2O)](PF6)25H2O 2 . Complex 2  was characterized; then photocatalytic studies were carried out in acidified acetonitrile. Surprisingly H2 could not be detected over a three hour period when complex 2  was utilized. This finding is in contrast to [Ru(pbt)2(L-pyr)Co(dmgBF2)2(H2O)](PF6)2.11H2O.1.5CH3COCH3 (where L-pyr = (4-pyridine)oxazolo[4,5-f]phenanthroline) which produced H2 at a rate of 80 uL h-1, or when the unreported complex, [Ru(pbt)2(L-CN)Co(dmgBF2)2(H2O)](PF6)2 (where L-CN = 4-(oxazolo[4,5-f][1,10]phenanthrolin-2-yl)benzonitrile) produced H2 at a rate of 50 uL h-1. Raman spectroscopic studies were carried out on [Co(dmgBF2)2(H2O)2], and complexes 1  and 2 , as well as time resolved spectroscopic measurements on complexes 1  and 2  in an effort to understand these differences in hydrogen production. It is interesting to note that bridging and terminal ligands can affect the production of hydrogen.

Photocatalytic hydrogen production with mixed-metal binuclear ruthenium(II)-cobalt(II) complexes: What a difference bridging and terminal ligands can make.

245th National Meeting (2013)

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